热喷涂制备Fe基非晶合金涂层的组织性能及其激光重熔行为的研究
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摘要
本文根据多组元非晶合金系设计理论，在Fe基非晶合金粉末中以W替换P，并采用大气等离子喷涂(APS)和超音速火焰喷涂(HVOF)工艺在Q235基体上制备了涂层，探索了在Fe基非晶合金涂层中以W替换P的可行性。针对涂层的多孔结构特征及其与基体间结合强度较低的问题，通过热处理和激光表面重熔技术对所制备的Fe基非晶合金涂层进行后处理，研究了Fe基非晶合金涂层晶化过程以及激光重熔过程中的组织、结构和性能的变化规律，并采用电化学工作站对Fe基非晶合金涂层在酸、碱、盐腐蚀介质中的耐蚀性能进行了研究。所获得的主要研究成果如下：
首先，通过对含W与含P的Fe基非晶合金涂层(分别编号为Fe-W和Fe-P)性能的研究，证明了在Fe基非晶合金涂层中以W替换P的优越性和可行性。研究表明Fe-W涂层的断裂韧性显著高于Fe-P涂层，两者的纳米压痕硬度相近；Fe-W晶化起始温度595.4℃比Fe-P提高33.4℃；Fe-W涂层在H2SO4、NaOH和NaCl腐蚀介质中的自腐蚀电流密度分别比Fe-P涂层降低了4.9%、28.6%和21%；并且在NaCl溶液中能形成稳定的钝化膜，自腐蚀电位比Fe-P提高了9倍。
其次，通过对Fe基非晶合金涂层进行激光表面重熔处理的研究，阐明了激光重熔合金区微观缺陷的产生机制，并提出了预测合金区高度的技术方案，为制定优化的激光表面重熔工艺方案提供了理论指导。研究表明当合金区高度小于喷涂态涂层厚度时，由于熔池底部与未熔涂层间粗糙的接触面阻碍了液态金属的流动，在熔池快速凝固过程中，内部气体残留于熔池中而形成直径大于50μm的圆形孔洞缺陷；进而由于应力集中和熔池凝固时引起的拉应力导致圆形空洞周围的合金区和未熔涂层中产生微裂纹。当重熔涂层合金区高度稍大于喷涂态涂层厚度时，合金区的微观缺陷最少，具有最优良的综合性能。通过自定义的孔隙修正系数α和激光能量有效利用率ξ分别对材料热物理性能和一维无限大平板热传导公式进行修正，可以较为准确的预测合金高度。
最后，通过对Fe基非晶合金涂层在NaOH溶液中耐蚀性能影响因素的研究，提出贡献率的概念，为非晶合金涂层的耐蚀性能提供了评价方法。研究表明非晶相含量、孔隙率、合金元素和表面粗糙度对Fe基非晶合金涂层自腐蚀电位贡献率的大小分别为57.1%，28.7%，14.2%和0%；对自腐蚀电流密度贡献率的大小分别为85.7%，13.1%，0.6%和0.6%。
In this dissertation, P was replaced by W in Fe-based amorphous alloy powderaccording to the multi-component amorphous alloy design theory, then the powderswere deposited onto Q235substrate through atmospheric plasma spray (APS) andhigh velocity oxgen-fuel spray (HVOF), and the feasibility of replacing P by W inFe-based a morphous a lloy c oatings w as di scussed. A imed a t p orous s tructurecharacteristics of the coating and lower bond strength of the coating and substrate, theFe-based a morphous a lloy c oatings w ere h eat t reated an d l aser su rface r emelted(LSM), and the crystallization and evolution rules of microhardness and propertiesduring processing were studied, and the corrosion resistance of Fe-based amorphousalloy coatings in acid, alkali and salt corrodents was investigated by electrochemicalwork station.
First, the feasibility of replacing P by W in Fe-based amorphous alloy coatings(designated as Fe-P and Fe-W, respectively) was demonstrated by investigating theproperties of Fe-based amorphous alloy coatings containing W and P, respectively.Research sh owed t hat t he f racture toughness o f F e-W coatings was s ignificantlyhigher than that of Fe-P coatings, the nano indentor hardness of the two was similar,the in itial crystallization te mperature of F e-W coatings was595.4℃which wa s33.4℃higher t han t hat of F e-P coatings, t he c orrosion current de nsity of Fe-Wcoatings in H2SO4, NaOH and NaCl corrodents were lowered by4.9%,28.6%and21%c omparing w ith t hose of F e-P coatings, respectively. Fe-W coatings couldestablish a stable passivation membrane in NaCl solution and its corrosion potentialwas9times higher than that of Fe-P coatings.
Secondly, mechanics of microdefects in L SM al loy ar ea w ere clarified a ndtechnical proposal of alloy height prediction was proposed through research of LSMFe-based amorphous alloy coatings which could provides a theoretical guidance forestablishment of optimized LSM processing scheme. Research showed that when thealloy height was less than the thickness of as s prayed coatings, since the flow ofliquid metal was blocked by t he rough contact surface of bottom LSM bath andunmelted c oatings, internal ga s w as r emained i n t he ba th dur ing r apid c ooling process and circular holes defects were formed, since the stress concentration andtensile stress formed by s olidification of the bath, microcracks were generated inalloy area and unmelted coatings. When alloy height was slightly greater than thethickness of as-sprayed coatings, the LSM coatings had the minimum quantity ofmicrodefects an d p ossessed t he b est co mprehensive p roperties. The alloy he ightcould be p redicted c omparatively exactly through r evising t he one-dimensionalinfinite plate heat conduction formula by self-defined porosity correction factor αand energy efficient utilization rate ξ.
Finally, the contributing ratio concept was proposed through affecting factorsinvestigation of corrosion resistance of Fe-based amorphous alloy coatings in NaOHsolution which provided an evaluation method for corrosion resistance of amorphousalloy coatings. Research showed that contributing ratios of amorphous phase content,porosity, alloy e lement a nd surface r oughness to c orrosion pot ential of F e-basedamorphous alloy c oating w ere57.1%,28.7%,14.2%and0%, respectively, a ndcontributing ratios to corrosion current density were85.7%,13.1%,0.6%and0.6%,respectively.
首先，通过对含W与含P的Fe基非晶合金涂层(分别编号为Fe-W和Fe-P)性能的研究，证明了在Fe基非晶合金涂层中以W替换P的优越性和可行性。研究表明Fe-W涂层的断裂韧性显著高于Fe-P涂层，两者的纳米压痕硬度相近；Fe-W晶化起始温度595.4℃比Fe-P提高33.4℃；Fe-W涂层在H2SO4、NaOH和NaCl腐蚀介质中的自腐蚀电流密度分别比Fe-P涂层降低了4.9%、28.6%和21%；并且在NaCl溶液中能形成稳定的钝化膜，自腐蚀电位比Fe-P提高了9倍。
其次，通过对Fe基非晶合金涂层进行激光表面重熔处理的研究，阐明了激光重熔合金区微观缺陷的产生机制，并提出了预测合金区高度的技术方案，为制定优化的激光表面重熔工艺方案提供了理论指导。研究表明当合金区高度小于喷涂态涂层厚度时，由于熔池底部与未熔涂层间粗糙的接触面阻碍了液态金属的流动，在熔池快速凝固过程中，内部气体残留于熔池中而形成直径大于50μm的圆形孔洞缺陷；进而由于应力集中和熔池凝固时引起的拉应力导致圆形空洞周围的合金区和未熔涂层中产生微裂纹。当重熔涂层合金区高度稍大于喷涂态涂层厚度时，合金区的微观缺陷最少，具有最优良的综合性能。通过自定义的孔隙修正系数α和激光能量有效利用率ξ分别对材料热物理性能和一维无限大平板热传导公式进行修正，可以较为准确的预测合金高度。
最后，通过对Fe基非晶合金涂层在NaOH溶液中耐蚀性能影响因素的研究，提出贡献率的概念，为非晶合金涂层的耐蚀性能提供了评价方法。研究表明非晶相含量、孔隙率、合金元素和表面粗糙度对Fe基非晶合金涂层自腐蚀电位贡献率的大小分别为57.1%，28.7%，14.2%和0%；对自腐蚀电流密度贡献率的大小分别为85.7%，13.1%，0.6%和0.6%。
In this dissertation, P was replaced by W in Fe-based amorphous alloy powderaccording to the multi-component amorphous alloy design theory, then the powderswere deposited onto Q235substrate through atmospheric plasma spray (APS) andhigh velocity oxgen-fuel spray (HVOF), and the feasibility of replacing P by W inFe-based a morphous a lloy c oatings w as di scussed. A imed a t p orous s tructurecharacteristics of the coating and lower bond strength of the coating and substrate, theFe-based a morphous a lloy c oatings w ere h eat t reated an d l aser su rface r emelted(LSM), and the crystallization and evolution rules of microhardness and propertiesduring processing were studied, and the corrosion resistance of Fe-based amorphousalloy coatings in acid, alkali and salt corrodents was investigated by electrochemicalwork station.
First, the feasibility of replacing P by W in Fe-based amorphous alloy coatings(designated as Fe-P and Fe-W, respectively) was demonstrated by investigating theproperties of Fe-based amorphous alloy coatings containing W and P, respectively.Research sh owed t hat t he f racture toughness o f F e-W coatings was s ignificantlyhigher than that of Fe-P coatings, the nano indentor hardness of the two was similar,the in itial crystallization te mperature of F e-W coatings was595.4℃which wa s33.4℃higher t han t hat of F e-P coatings, t he c orrosion current de nsity of Fe-Wcoatings in H2SO4, NaOH and NaCl corrodents were lowered by4.9%,28.6%and21%c omparing w ith t hose of F e-P coatings, respectively. Fe-W coatings couldestablish a stable passivation membrane in NaCl solution and its corrosion potentialwas9times higher than that of Fe-P coatings.
Secondly, mechanics of microdefects in L SM al loy ar ea w ere clarified a ndtechnical proposal of alloy height prediction was proposed through research of LSMFe-based amorphous alloy coatings which could provides a theoretical guidance forestablishment of optimized LSM processing scheme. Research showed that when thealloy height was less than the thickness of as s prayed coatings, since the flow ofliquid metal was blocked by t he rough contact surface of bottom LSM bath andunmelted c oatings, internal ga s w as r emained i n t he ba th dur ing r apid c ooling process and circular holes defects were formed, since the stress concentration andtensile stress formed by s olidification of the bath, microcracks were generated inalloy area and unmelted coatings. When alloy height was slightly greater than thethickness of as-sprayed coatings, the LSM coatings had the minimum quantity ofmicrodefects an d p ossessed t he b est co mprehensive p roperties. The alloy he ightcould be p redicted c omparatively exactly through r evising t he one-dimensionalinfinite plate heat conduction formula by self-defined porosity correction factor αand energy efficient utilization rate ξ.
Finally, the contributing ratio concept was proposed through affecting factorsinvestigation of corrosion resistance of Fe-based amorphous alloy coatings in NaOHsolution which provided an evaluation method for corrosion resistance of amorphousalloy coatings. Research showed that contributing ratios of amorphous phase content,porosity, alloy e lement a nd surface r oughness to c orrosion pot ential of F e-basedamorphous alloy c oating w ere57.1%,28.7%,14.2%and0%, respectively, a ndcontributing ratios to corrosion current density were85.7%,13.1%,0.6%and0.6%,respectively.
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